Color photographic developing method and developer therefor

ABSTRACT

In a color photographic developing method of silver halide color photographic materials by developing said materials with a developer solution containing 4-amino-3-methyl-N-ethyl-N-( Beta methanesulfonamidoethyl)aniline sesquisulfate monohydrate as a developing agent, the crystallization of the developing agent in the developer solution is prevented by incorporating at least one crystallization preventing agent selected from the group consisting of lactose and hydroxypropylmethyl cellulose into the developer solution.

United States Patent [191 Hasegawa et al.

[ Dec. 18, 1973 COLOR PHOTOGRAPHIC DEVELOPING METHOD AND DEVELOPER THEREFOR Inventors: Fumio Hasegawa; Takeo Emoto;

Satoshi Kurihara, all of Kanagawa, Japan Fuji Photo Film Co., Ltd., Kanagawa, Japan Filed: Aug. 18, 1972 Appl. N0.: 281,673

Assignee:

Foreign Application Priority Data Aug. 20, 1971 Japan 46/63432 US. Cl 96/66 R, 96/66.4, 96/22, 96/55 XR Int. Cl G03c 5/30, G03c 7/16 Field of Search 96/66.4, 22, 166, 96/66 References Cited UNITED STATES PATENTS 8/1937 Russell 96/66.4

2,138,486 11/1938 Fournes 6/66.4 2,193,015 3/1940 Weissberger 96/66 R 2,366,496 1/1945 Dawson 96/66.4 3,615,497 10/1971 Fassbender 96/66.l

OTHER PUBLICATIONS Chem. Absts. Vol. 51, l3627e-f-g.

Primary Examiner-Norman G. Torchin Assistant Examiner-M. F. Kelley Att0rneyRichard C. Sughrue et al.

[57] ABSTRACT 6 Claims, No Drawings COLOR PHOTOGRAPHIC DEVELOPING METHOD AND DEVELOPER THEREFOR BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION This invention relates to a color photographic developing method and a developer therefor and, more particularly, it relates to a method for developing a silver halide color photographic material with a developer containing 4-amino-3-methyl-N-ethyl-N-([3- methanesulfonamidoethyl)aniline sesquisulfate monohydrate (hereinafter referred to as a developing agent) and a crystallization preventing agent for an amine base of the developing agent.

2. DESCRIPTION OF THE PRIOR ART As described in prior arts, it is known that an amine base of the developing agent cannot advantageously be used because it is crystallized out at a low temperature. This disadvantage is due to the salt out of the developing agent by an inorganic substance such as sodium carbonate or sodium sulfate incorporated in the developer solution.

An object of the present invention is therefore to provide a color developing method without accompanying with the crystallization of the developing agent. v

Another object of the present invention is to provide a color photographic developer of which the crystallization is prevented.

SUMMARY OF THE INVENTION As a result of research for eliminating the abovedescribed disadvantage, it was found that the above objects can be attained by incorporating at least a member selected from the group consisting of lactose and hydroxypropylmethyl cellulose as a crystallizationpreventing agent into a color photographic developer solution containing the developing agent.

Generally, crystallization-preventing agents must have an appropriate solubility in photographic developer solution and must not adversely effect the photographic properties of the color photographic materials to be developed. In these points, lactose and hydroxy propylmethyl cellulose are preferable crystallizationpreventing agents because they satisfy the above requirements. For example, hydroxylpropylmethyl cellulose used in the present invention has less tendency to be salted out in the developer solution than methyl cellulose described in the specification of Japapese Patent Publication No. 41,476/71. That is, while the addition of methyl cellulose in an amount of more than 0.7 percent by weight based on the developing agent to the developer solution increases the crystallizationpreventing effect, methyl cellulose per se is salted out to produce the precipitate thereof. On the other hand, hydroxypropylmethyl cellulose is not salted out even it if is added in an amount of 1 percent by weight based on the developing agent. The crystallization-preventing agent of the invention can be incorporated in the powder form into the developing agent in the form of powder, particle or granule, or can be incorporated as a powder form or an aqueous solution into the developer solution at any stage, for example, in preparing the developer solution or after the developer solution has been prepared for use.

The amount of the crystallization-preventing agent can range from 0.1 to 1.0 percent by weight, preferably from 0.4 to 1.0 percent by weight based on the developing agent.

A photographic developer solution of the present invention may contain conventional photographic additives such as preservatives, development-promoting agents, development inhibitors, antifoggants or alkalis.

EXAMPLE 1 A sensitometric exposure using a sensitometer was applied to a multiple-layer color negative film containing an anti-diffusion color coupler.

Then, three pieces of the color negative film thus exposed were subjected to a developing treatment using three kinds of developer solution, i.e., Developer A without any crystallization-preventing agent added and which was prepared for the purposes of comparison, Developer B containing lactose, and Developer C containing hydroxypropylmethyl cellulose.

Treating Process Temperature Time I. Color Development 20C 10 min. 2. First Fixation 20C 5 min. 3. Rinsing l6-20C 5 min. 4. Bleaching 20C 5 min. 5. Rinsing l620C 5 min. 6. Second Fixation 20C 5 min. 7. Rinsing l6-20C 8 min. 8. Drying Below 35C The compositions of the Developers A, B, and C employed in the above treatment were as follows;

DEVELOPER A Anhydrous Sodium Sulfite 2.0 g Developing Agent 5.0 g Sodium Carbonate (monohydrate) 50 g Potassium Bromide 2.0 g Sodium Hydroxide L0 g Water was added to make 1.0 l of solution DEVELOPER B The same composition as Developer A was employed except 1.0 percent by weight of lactose based on the developing agent was additionally added.

DEVELOPER C The same composition as Developer A was employed except l.0 percent by weight of hydroxypropylmethyl cellulose based on the developing agent was additionally added.

The results of the development employing Developers A, B, and C were such that there were no differences between each of the developers with respect to the red, green, and blue relative sensitivity, gamma 6), and fog, respectively, as a result of the differences between the Developers A, B, and C, and the resulting photographic properties were normal, respectively.

EXAMPLE 2 A developer solution was prepared employing the same kind of developing agent used in Example I in accordance with the following formulation. In the course of the preparation of the developer solution, lactose and/or hydroxypropylmethyl cellulose was added in several different quantities, respectively. Each of the resulting developer solutions was settled at a tempera ture of from 15 to 16C.

Developer Composition Water (25 30C) 800ml Anhydrous Sodium Sulfite 2.0 g

Crystallization Preventing Agent Lactose 0.03 7 g-0.065 g or Hydroxypropylmethyl Cellulose 0.0065 g Developing Agent 6.5 g Sodium Carbonate (Monohydrate) 60 g Potassium Bromide 2.0 g Sodium Hydroxide 1.0 g Water was added to make 1.0 l of solution (1) Commercially available lactose according to the pharmacopoeia of the amount of the developing agent was employed.

(2) l g of hydroxypropylmethyl cellulose was dissolved in 50 ml of water to obtain solution. O.l, 0.05, and 1.0 percent each of the resulting solution based on the developing agent was added thereto.

the viscosity of a 2 percent aqueous solution of hydroxypropylmethyl cellulose at a temperature of C was 7.2 4.8 CPS.

(3) The developing agent was prepared through decoloration with activated charcoal and recrystallization in a dilute sulfuric acid methanol from which the developing agent could be easily salted out.

The results of the effects for preventing the crystallization of the developing agent are shown in the following table from which it can be understood that the solubility of the developing agent was elevated by adding the lactose and/or the hydroxypropylmethyl cellulose, whereby crystallization of the developing agent was effectively prevented.

TABLE Time required for Separating Crystals of Amine Base (16C) (hrs) Crystallization Note Preventing Agent A large amount of developing agent crystallized out Without Addition While the invention has been described in detail and with reference to specific embodiments thereof. it will be apparent that various changes and modifications can be made therein without departing from the spirit scope thereof.

What is claimed is:

1. In a color photographic developing method of silver halide color photographic materials by developing said materials with a developer solution containing 4- amino-3-methyl-N-ethyl-N-(B-methanesulfonamidoethyl)aniline sesquisulfate monohydrate as a developing agent, the improvement which comprises preventing the crystallization of the developing agent in the developer solution by incorporating at least one crystallization-preventing agent selected from the group consisting of lactose and hydroxypropylmethyl cellulose into the developer solution.

2. The method as claimed in claim 1, wherein the amount of said crystallization-preventing agent is in the range of from 0.1 to 1.0 percent by weight based on the weight of said developing agent.

3. The method as claimed in claim 2, wherein said amount is from 0.4 to L0 percent by weight based on the weight of said developing agent.

4. A color developer solution comprising 4-amino-3- methyl-N-ethyl-N-(B-methanesulfonamidoethyl)aniline sesquisulfate monohydrate as a developing agent and at least one crystallization-preventing agent selected from the group consisting of lactose and hydroxypropylmethyl cellulose.

5. The color developer solution as claimed in claim 4, wherein the amount of said crystallizationpreventing agent is in the range of from 0.1 to 1.0 percent by weight based on the weight of said developing agent.

6. The color developer solution as claimed in claim 5,-wherein said amount is from 0.4 to 1.0 percent by weight based on the weight of said developing agent. 

2. The method as claimed in claim 1, wherein the amount of said crystallization-preventing agent is in the range of from 0.1 to 1.0 percent by weight based on the weight of said developing agent.
 3. The method as claimed in claim 2, wherein said amount is from 0.4 to 1.0 percent by weight based on the weight of said developing agent.
 4. A color developer solution comprising 4-amino-3-methyl-N-ethyl-N-( Beta -methanesulfonamidoethyl)aniline sesquisulfate monohydrate as a developing agent and at least one crystallization-preventing agent selected from the group consisting of lactose and hydroxypropylmethyl cellulose.
 5. The color developer solution as claimed in claim 4, wherein the amount of said crystallization-preventing agent is in the range of from 0.1 to 1.0 percent by weight based on the weight of said developing agent.
 6. The color developer solution as claimed in claim 5, wherein said amount is from 0.4 to 1.0 percent by weight based on the weight of said developing agent. 